CA2559831C - Ageing-resistant copolymers comprising polyamide blocks and polyether blocks - Google Patents
Ageing-resistant copolymers comprising polyamide blocks and polyether blocks Download PDFInfo
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- CA2559831C CA2559831C CA 2559831 CA2559831A CA2559831C CA 2559831 C CA2559831 C CA 2559831C CA 2559831 CA2559831 CA 2559831 CA 2559831 A CA2559831 A CA 2559831A CA 2559831 C CA2559831 C CA 2559831C
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a copolymer composition comprising homo- or copolyamide polyamide blocks and polyether blocks and further comprising: a) 3 000 to 8 000 ppm of at least one phenolic antioxidant; b) 0 to 5000 ppm of at least one phosphorus or sulphur based antioxidant; c) 0 to 5000 ppm of at least one UV absorber;and d) 200 to 3000 ppm of at least one methylated HALS meaning hindered amine light stabilizer and/or 200 to 800 ppm of at least one nonmethylated HALS; ppm meaning parts per million of total composition. The compositions are useful in mainufacturing articles, such as shoe sole.
Description
AGEING-RESISTANT COPOLYMERS COMPRISING POLYAMIDE BLOCKS
AND POLYETHER BLOCKS
The present invention relates to copolymers comprising polyamide blocks and polyether blocks which are resistant to ageing and more particularly to ageing due to heat and/or UV (ultraviolet) radiation. Copolymers comprising polyamide blocks and polyether blocks are also known as poly(ether-block-amides (PEBA): they are thermoplastic elastomers. They are also known as polyamide elastomers. These copolymers are of use in manufacturing objects such as shoe soles, in particular of sports shoes.
The prior arts have disclosed numerous copolymers comprising polyamide blocks and polyether blocks and numerous uses of these copolymers. Antioxidants and UV
inhibitors are mentioned in these prior arts. The document JP-61-289119-A1 discloses PEBA compositions additivated with one or more additives for improving the light and heat stability, it being possible for the light stabilizer to be hindered amine compounds.
However, it is found that many mixtures of additives protect against oxidation and UV radiation but cause an unsightly yellowing of the final composition characterized by a yellow index, abbreviated to YI.
It has now been discovered that not just any antioxidant or any UV inhibitor can be used if it is desired to obtain a composition with a low yellow index. This is because at least two additives are necessary: (a) a phenolic antioxidant and (d) a hindered amine light stabilizer or HALS, and it is necessary for the said HALS to be present in the composition in very precise proportions, especially if it is nonmethylated.
The present invention relates to a composition based on a PEBA copolymer, that is to say a copolymer comprising homo- or copolyamide polyamide blocks (abbreviated to PA blocks), with the exclusion of completely aromatic PA blocks, and polyether blocks (abbreviated to PE
blocks) comprising:
a) 500 to 10 000 ppm of at least one phenolic antioxidant;
b) 0 to 5000 ppm of at least one antioxidant based on phosphorus or based on sulphur;
c) 0 to 5000 ppm of at least one UV absorber;
d) 200 to 3000 ppm of at least one methylated hindered amine light stabilizer or HALS and/or 200 to 1300 ppm of at least one nonmethylated hindered amine light stabilizer or HALS;
ppm meaning parts per million of total composition.
It would not be departing from the scope of the invention to replace at least two of these additives (a) to (d) by a single additive (a), (b), (c) or (d) fulfilling the same functions as the said single additives.
These functions can be:
~ function of phenolic antioxidant (a);
~ function of antioxidant based on phosphorus or based on sulphur (b);
~ function of UV absorber (c);
~ function of hindered amine light stabilizer (d).
For example, Tunuvin 144 fulfils both a function of phenolic antioxidant and a function of hindered amine light stabilizer.
These additives can be introduced into the PEBA
copolymers during their synthesis or subsequently, by dry blending, or into the said PEBA copolymers in the melt. Advantageously, a masterbatch of these additives is prepared, that is to say a resin, preferably of PEBA
copolymer or copolyamide type, for example comprising 10 to 30o by weight of these additives, and then this masterbatch is added in a proportion of a few percent to the PEBA copolymers which it is desired to stabilize. This masterbatch can be manufactured according to the usual techniques for thermoplastics by introducing the additives into the PEBA copolymers in the melt in an extruder or any equivalent device.
Advantageously, the proportion of (a) is between 2000 and 8000 ppm and preferably between 3000 and 6000.
Advantageously, the proportion of (b) is between 1000 and 2000 ppm and preferably between 1200 and 1700.
Advantageously, the proportion of (c) is between 1000 and 2000 ppm and preferably between 1200 and 1700.
Advantageously, the proportion of HALS (d), when the latter is methylated, is between 200 and 3000 ppm, preferably between 300 and 2000, more preferably still between 400 and 1000 and, when the latter is nonmethylated, is between 200 and 1300 ppm, preferably between 200 and 800, more preferably still between 300 and 700.
The PEBA copolymers result from the copolycondensation of polyamide sequences comprising reactive ends with polyether sequences comprising reactive ends, the said polyamide sequences being aliphatic or semi-aromatic, the completely aromatic polyamide sequences with which the document EP 608 976 is concerned being expressly excluded from our invention.
It is a matter of, inter alias 1) Polyamide sequences comprising diamine chain ends with polyoxyalkylene sequences comprising dicarboxyl chain ends.
2) Polyamide sequences comprising dicarboxyl chain ends with polyoxyalkylene sequences comprising diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic a,w-dihydroxylated polyoxyalkylene sequences known as polyetherdiols.
3) Polyamide sequences comprising dicarboxyl chain ends with polyetherdiols, the products obtained being, in this specific case, polyetherester amides. The copolymers of the invention are advantageously of this type.
The polyamide sequences comprising dicarboxyl chain ends originate, for example, from the condensation of precursors of polyamides in the presence of a chain-limiting dicarboxylic acid.
The polyamide sequences comprising diamine chain ends originate, for example, from the condensation of precursors of polyamides in the presence of a chain-limiting diamine.
The PEBA polymers can also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and of the precursors of the polyamide blocks.
For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer is obtained which has essentially polyether blocks and polyamide blocks, the latter being of highly variable length, but also the various reactants which have reacted randomly, which are distributed randomly (statistically) along the polymer chain.
Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted. A polymer is obtained which has essentially polyether blocks and polyamide blocks, the latter being of highly variable length, but also the various reactants which have reacted randomly, which are distributed randomly (statistically) along the polymer chain.
The polyether blocks (PE blocks) can represent 5 to 850 by weight of the copolymer comprising polyamide and polyether blocks. The polyether blocks are composed of alkylene oxide units. These units can, for example, be ethylene oxide units, propylene oxide units, trimethylene ether units (such copolymers with poly(trimethylene ether) blocks are disclosed in the Patent US 6 590 065) or tetrahydrofuran units (which results in poly(tetramethylene glycol) series). PEG
blocks, that is to say those composed of ethylene oxide units, PPG blocks, that is to say those composed of propylene oxide units, poly(trimethylene ether) blocks and PTMG blocks, that is to say those composed of . tetramethylene glycol units, also known as polytetrahydrofuran blocks, are thus used. The PEBA
copolymers can comprise several types of polyethers in their chain. Mention may also be made of block or random copolyethers. The amount of polyether blocks in these PEBA copolymers is advantageously from 10 to 70 0 by weight of the copolymer and preferably from 35 to 600.
The polyetherdiol blocks are either used as is and copolycondensed with polyamide blocks comprising carboxyl ends or are aminated, in order to be converted to polyetherdiamines, and condensed with polyamide blocks comprising carboxyl ends. They can also be mixed with polyamide precursors and a chain-limiting diacid in order to prepare polymers comprising polyamide blocks and polyether blocks having randomly distributed units.
The number-average molar mass Mn of the polyamide sequences can be between 500 and 10 000 and preferably between 500 and 6000. The mass Mn of the polyether sequences can be between 100 and 6000 and preferably between 200 and 3000.
These PEBA polymers, whether they originate from the copolycondensation of polyamide and polyether sequences prepared beforehand or from a one-stage reaction, exhibit, for example, an intrinsic viscosity between 0.8 and 2.5, measured in meta-cresol at 25°C for an initial concentration of 0.5 g per 100 g 0.8 g/100 ml.
The preparation of these copolymers is described in the prior art. Mention may be made, for example, of Patents WO 04/037898, EP 1 262 527, EP 1 270 211, EP 1 136 512, EP 1 046 675, EP 1 057 870, EP 1 155 065, EP 506 495 and EP 504 058.
The invention is of particular use for PEBA polymers which have PA 12, PA 11 or PA 6 PA blocks and PTMG, PEG
or PPG PE blocks. The polyamide blocks can be copolyamides.
As regards the phenolic antioxidant (a), mention may be made, as examples, of Irganox~ 1010, Irganox~ 1098 and Irganox~ 245. These are hindered phenols.
As regards the antioxidant of phosphite type or based on sulphur (b), mention may be made, as examples, of ADK STAB~ PEP 36, ADK STAB~ PEPBHT from Adeka Palmarole and Doverphos~ 9228 from Dover Chemical.
As regards the UV absorber, mention may be made, as examples, of Tinuvin~ 320, Tinuvin~ 350, Tinuvin~ 312 from CIBA.
As regards the hindered amine light stabilizer abbreviated to HALS (d), its content in the final composition should be relatively low in order to limit the negative impact on the YI during thermal tests or in order to limit the interaction with hindered phenols. The absense of HALS in the composition (with or without UV absorber in the composition) significantly reduces the UV resistance.
Mention may be made, as methylated HALS, of Tinuvin~
765 and Tinuvin~ 144 from CIBA, ADK STAB~ LA52 from _ 7 Adeka Palmarole and Chimasorb~ 119 from CIBA. Mention may be made, as nonmethylated HALS, of Tinuvin~ 770 from CIBA and Nylostab~ SEED from Clariant. Preferably, it is a methylated HALS, more effective than a nonmethylated HALS.
The mass of the HALS (between 500 and 1000 g/mol) may not be excessively high, in order for the latter to be able to migrate into the surface . However, in the case of a transparent matrix, the mass of the HALS may be higher since it has to be present throughout and therefore does not have to migrate.
All these additives are described in "Stabilization of Polymeric Materials", Zweifel, H., 1998, Springer-Verlag, Berlin Heidelberg New York, ISBN: 354061690X.
The PEBA copolymer compositions can comprise, in addition to the preceding additives, plasticizers, fillers or colorants.
Use was made of a copolymer comprising polyamide blocks of PA 12 type and polyether blocks of PTMG type, referred to as PEBA l, to which various combinations of additives (a) to (d) were added in the melt, at various contents, in order to manufacture compositions M1 to M11 of Table 1 below. The proportions of additives in Table 1 are expressed in parts per 106 parts of total mixture (PEBA + additives). The various compositions were subsequently tested for their resistance to thermal oxidation and to photo-oxidation.
In the first case (thermal oxidation), 100 x 100 X 1 mm3 plaques were placed in an oven at 90°C and the change in the coloration was measured. For this, the YI of plaques with compositions M1, M2, M4, M6, M7, M8 (see graphs 1 and 2) is measured with the following parameters: illuminant D65/observer 10°.
In the second case (photo-oxidation), 100 x 100 x 1 mm3 plaques were placed in a Sepap~ 12.24 chamber and the time necessary for the appearance of surface cracking is measured; this time is denoted by "UV resistance" in Table 1.
The change in the Yellow Index, abbreviated to YI (on the ordinate), of the compositions M1 to M11 during 2 tests carried out separately as a function of the exposure time, expressed in days, is shown in Graphs 1 and 2 below. In Graph 1, the YI has been represented successively from left to right at to (initial time), to + 7 days, to + 14 days, to + 21 days and to + 34 days for each composition M during a first test. In Graph 2, the YI has been represented successively from left to right at to (initial time), to + 7 days, to + 14 days, to + 21 days and to +, 30 days for each composition M
during a second test.
It is observed that the reduction in the content of HALS (see M9 vs. M5) makes it possible to reduce the change in the YI. However, the use of methylated HALS
(M8, M10 and M11) or the absence of HALS (M3, M7) is even more effective in limiting the change in the YI.
However, Table 1 shows that, in order to maintain a good UV resistance, the presence of HALS is necessary, hence the good UV/yellow index compromise obtained using very little nonmethylated HALS and/or a methylated HALS.
0 0 0 o O
i ~, u7 ~ u7 ~'r~ r1 r1 0 0 ~ o o O
O o y o 0 o O
n u~ ~ CO
0 0 0 o O
O~o o O o O
u7~ ~n M
O O p p COO O o O
O O p r-- -I
O o o O
L~o 0 o "~
O O O O
~Oo 0 0 0 O O u7 O
0 0 o O O
1no 0 o O
~ O ~ r1 u7 r1H
n I
O
I ~ o O O o O
0 0 o O O
H ,~,'~' o o ~n r1 n O O O
O o p O O
O
O O O O O
O O O O O
u7 u7 O ri (r) r-I ~-I N
n O O
r1O
O
N
01f~ N (~ CDQp N O O O N O r-IW ~ W W
r1 ' ~ W FCW W
O O N ~ rlI~~' U) HlW W 1 i r1 M C~ M t~'~ ~ x cex rx ~ ~ ~ ~ ~ ~ ~ ~ W Pa PaO N
~ x ~ s~ ~ ~ ~ o ra f11O -r-I-rl-.-I-~i-rlu1a.-)E-~E-~H , O s~ ~ D 5 ~ D N cn cl~cn U1S-itll (1, ~ ~ ~ ~ ~ ~ O N N
rd S~~ s~ - f.1 O -r-I-r-I-r-I-r-I-r-I,~~ 1 1 1 O
~.IH H H H H ~ z - 1~ -Graph 1 so ,o so tp 2p +, aa.
pfp +
days O
tp +
dpt tp+34Mqs ~, Gr-aph 2 so ,o so 50 ~ 2p ~ tp +
AND POLYETHER BLOCKS
The present invention relates to copolymers comprising polyamide blocks and polyether blocks which are resistant to ageing and more particularly to ageing due to heat and/or UV (ultraviolet) radiation. Copolymers comprising polyamide blocks and polyether blocks are also known as poly(ether-block-amides (PEBA): they are thermoplastic elastomers. They are also known as polyamide elastomers. These copolymers are of use in manufacturing objects such as shoe soles, in particular of sports shoes.
The prior arts have disclosed numerous copolymers comprising polyamide blocks and polyether blocks and numerous uses of these copolymers. Antioxidants and UV
inhibitors are mentioned in these prior arts. The document JP-61-289119-A1 discloses PEBA compositions additivated with one or more additives for improving the light and heat stability, it being possible for the light stabilizer to be hindered amine compounds.
However, it is found that many mixtures of additives protect against oxidation and UV radiation but cause an unsightly yellowing of the final composition characterized by a yellow index, abbreviated to YI.
It has now been discovered that not just any antioxidant or any UV inhibitor can be used if it is desired to obtain a composition with a low yellow index. This is because at least two additives are necessary: (a) a phenolic antioxidant and (d) a hindered amine light stabilizer or HALS, and it is necessary for the said HALS to be present in the composition in very precise proportions, especially if it is nonmethylated.
The present invention relates to a composition based on a PEBA copolymer, that is to say a copolymer comprising homo- or copolyamide polyamide blocks (abbreviated to PA blocks), with the exclusion of completely aromatic PA blocks, and polyether blocks (abbreviated to PE
blocks) comprising:
a) 500 to 10 000 ppm of at least one phenolic antioxidant;
b) 0 to 5000 ppm of at least one antioxidant based on phosphorus or based on sulphur;
c) 0 to 5000 ppm of at least one UV absorber;
d) 200 to 3000 ppm of at least one methylated hindered amine light stabilizer or HALS and/or 200 to 1300 ppm of at least one nonmethylated hindered amine light stabilizer or HALS;
ppm meaning parts per million of total composition.
It would not be departing from the scope of the invention to replace at least two of these additives (a) to (d) by a single additive (a), (b), (c) or (d) fulfilling the same functions as the said single additives.
These functions can be:
~ function of phenolic antioxidant (a);
~ function of antioxidant based on phosphorus or based on sulphur (b);
~ function of UV absorber (c);
~ function of hindered amine light stabilizer (d).
For example, Tunuvin 144 fulfils both a function of phenolic antioxidant and a function of hindered amine light stabilizer.
These additives can be introduced into the PEBA
copolymers during their synthesis or subsequently, by dry blending, or into the said PEBA copolymers in the melt. Advantageously, a masterbatch of these additives is prepared, that is to say a resin, preferably of PEBA
copolymer or copolyamide type, for example comprising 10 to 30o by weight of these additives, and then this masterbatch is added in a proportion of a few percent to the PEBA copolymers which it is desired to stabilize. This masterbatch can be manufactured according to the usual techniques for thermoplastics by introducing the additives into the PEBA copolymers in the melt in an extruder or any equivalent device.
Advantageously, the proportion of (a) is between 2000 and 8000 ppm and preferably between 3000 and 6000.
Advantageously, the proportion of (b) is between 1000 and 2000 ppm and preferably between 1200 and 1700.
Advantageously, the proportion of (c) is between 1000 and 2000 ppm and preferably between 1200 and 1700.
Advantageously, the proportion of HALS (d), when the latter is methylated, is between 200 and 3000 ppm, preferably between 300 and 2000, more preferably still between 400 and 1000 and, when the latter is nonmethylated, is between 200 and 1300 ppm, preferably between 200 and 800, more preferably still between 300 and 700.
The PEBA copolymers result from the copolycondensation of polyamide sequences comprising reactive ends with polyether sequences comprising reactive ends, the said polyamide sequences being aliphatic or semi-aromatic, the completely aromatic polyamide sequences with which the document EP 608 976 is concerned being expressly excluded from our invention.
It is a matter of, inter alias 1) Polyamide sequences comprising diamine chain ends with polyoxyalkylene sequences comprising dicarboxyl chain ends.
2) Polyamide sequences comprising dicarboxyl chain ends with polyoxyalkylene sequences comprising diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic a,w-dihydroxylated polyoxyalkylene sequences known as polyetherdiols.
3) Polyamide sequences comprising dicarboxyl chain ends with polyetherdiols, the products obtained being, in this specific case, polyetherester amides. The copolymers of the invention are advantageously of this type.
The polyamide sequences comprising dicarboxyl chain ends originate, for example, from the condensation of precursors of polyamides in the presence of a chain-limiting dicarboxylic acid.
The polyamide sequences comprising diamine chain ends originate, for example, from the condensation of precursors of polyamides in the presence of a chain-limiting diamine.
The PEBA polymers can also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and of the precursors of the polyamide blocks.
For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer is obtained which has essentially polyether blocks and polyamide blocks, the latter being of highly variable length, but also the various reactants which have reacted randomly, which are distributed randomly (statistically) along the polymer chain.
Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted. A polymer is obtained which has essentially polyether blocks and polyamide blocks, the latter being of highly variable length, but also the various reactants which have reacted randomly, which are distributed randomly (statistically) along the polymer chain.
The polyether blocks (PE blocks) can represent 5 to 850 by weight of the copolymer comprising polyamide and polyether blocks. The polyether blocks are composed of alkylene oxide units. These units can, for example, be ethylene oxide units, propylene oxide units, trimethylene ether units (such copolymers with poly(trimethylene ether) blocks are disclosed in the Patent US 6 590 065) or tetrahydrofuran units (which results in poly(tetramethylene glycol) series). PEG
blocks, that is to say those composed of ethylene oxide units, PPG blocks, that is to say those composed of propylene oxide units, poly(trimethylene ether) blocks and PTMG blocks, that is to say those composed of . tetramethylene glycol units, also known as polytetrahydrofuran blocks, are thus used. The PEBA
copolymers can comprise several types of polyethers in their chain. Mention may also be made of block or random copolyethers. The amount of polyether blocks in these PEBA copolymers is advantageously from 10 to 70 0 by weight of the copolymer and preferably from 35 to 600.
The polyetherdiol blocks are either used as is and copolycondensed with polyamide blocks comprising carboxyl ends or are aminated, in order to be converted to polyetherdiamines, and condensed with polyamide blocks comprising carboxyl ends. They can also be mixed with polyamide precursors and a chain-limiting diacid in order to prepare polymers comprising polyamide blocks and polyether blocks having randomly distributed units.
The number-average molar mass Mn of the polyamide sequences can be between 500 and 10 000 and preferably between 500 and 6000. The mass Mn of the polyether sequences can be between 100 and 6000 and preferably between 200 and 3000.
These PEBA polymers, whether they originate from the copolycondensation of polyamide and polyether sequences prepared beforehand or from a one-stage reaction, exhibit, for example, an intrinsic viscosity between 0.8 and 2.5, measured in meta-cresol at 25°C for an initial concentration of 0.5 g per 100 g 0.8 g/100 ml.
The preparation of these copolymers is described in the prior art. Mention may be made, for example, of Patents WO 04/037898, EP 1 262 527, EP 1 270 211, EP 1 136 512, EP 1 046 675, EP 1 057 870, EP 1 155 065, EP 506 495 and EP 504 058.
The invention is of particular use for PEBA polymers which have PA 12, PA 11 or PA 6 PA blocks and PTMG, PEG
or PPG PE blocks. The polyamide blocks can be copolyamides.
As regards the phenolic antioxidant (a), mention may be made, as examples, of Irganox~ 1010, Irganox~ 1098 and Irganox~ 245. These are hindered phenols.
As regards the antioxidant of phosphite type or based on sulphur (b), mention may be made, as examples, of ADK STAB~ PEP 36, ADK STAB~ PEPBHT from Adeka Palmarole and Doverphos~ 9228 from Dover Chemical.
As regards the UV absorber, mention may be made, as examples, of Tinuvin~ 320, Tinuvin~ 350, Tinuvin~ 312 from CIBA.
As regards the hindered amine light stabilizer abbreviated to HALS (d), its content in the final composition should be relatively low in order to limit the negative impact on the YI during thermal tests or in order to limit the interaction with hindered phenols. The absense of HALS in the composition (with or without UV absorber in the composition) significantly reduces the UV resistance.
Mention may be made, as methylated HALS, of Tinuvin~
765 and Tinuvin~ 144 from CIBA, ADK STAB~ LA52 from _ 7 Adeka Palmarole and Chimasorb~ 119 from CIBA. Mention may be made, as nonmethylated HALS, of Tinuvin~ 770 from CIBA and Nylostab~ SEED from Clariant. Preferably, it is a methylated HALS, more effective than a nonmethylated HALS.
The mass of the HALS (between 500 and 1000 g/mol) may not be excessively high, in order for the latter to be able to migrate into the surface . However, in the case of a transparent matrix, the mass of the HALS may be higher since it has to be present throughout and therefore does not have to migrate.
All these additives are described in "Stabilization of Polymeric Materials", Zweifel, H., 1998, Springer-Verlag, Berlin Heidelberg New York, ISBN: 354061690X.
The PEBA copolymer compositions can comprise, in addition to the preceding additives, plasticizers, fillers or colorants.
Use was made of a copolymer comprising polyamide blocks of PA 12 type and polyether blocks of PTMG type, referred to as PEBA l, to which various combinations of additives (a) to (d) were added in the melt, at various contents, in order to manufacture compositions M1 to M11 of Table 1 below. The proportions of additives in Table 1 are expressed in parts per 106 parts of total mixture (PEBA + additives). The various compositions were subsequently tested for their resistance to thermal oxidation and to photo-oxidation.
In the first case (thermal oxidation), 100 x 100 X 1 mm3 plaques were placed in an oven at 90°C and the change in the coloration was measured. For this, the YI of plaques with compositions M1, M2, M4, M6, M7, M8 (see graphs 1 and 2) is measured with the following parameters: illuminant D65/observer 10°.
In the second case (photo-oxidation), 100 x 100 x 1 mm3 plaques were placed in a Sepap~ 12.24 chamber and the time necessary for the appearance of surface cracking is measured; this time is denoted by "UV resistance" in Table 1.
The change in the Yellow Index, abbreviated to YI (on the ordinate), of the compositions M1 to M11 during 2 tests carried out separately as a function of the exposure time, expressed in days, is shown in Graphs 1 and 2 below. In Graph 1, the YI has been represented successively from left to right at to (initial time), to + 7 days, to + 14 days, to + 21 days and to + 34 days for each composition M during a first test. In Graph 2, the YI has been represented successively from left to right at to (initial time), to + 7 days, to + 14 days, to + 21 days and to +, 30 days for each composition M
during a second test.
It is observed that the reduction in the content of HALS (see M9 vs. M5) makes it possible to reduce the change in the YI. However, the use of methylated HALS
(M8, M10 and M11) or the absence of HALS (M3, M7) is even more effective in limiting the change in the YI.
However, Table 1 shows that, in order to maintain a good UV resistance, the presence of HALS is necessary, hence the good UV/yellow index compromise obtained using very little nonmethylated HALS and/or a methylated HALS.
0 0 0 o O
i ~, u7 ~ u7 ~'r~ r1 r1 0 0 ~ o o O
O o y o 0 o O
n u~ ~ CO
0 0 0 o O
O~o o O o O
u7~ ~n M
O O p p COO O o O
O O p r-- -I
O o o O
L~o 0 o "~
O O O O
~Oo 0 0 0 O O u7 O
0 0 o O O
1no 0 o O
~ O ~ r1 u7 r1H
n I
O
I ~ o O O o O
0 0 o O O
H ,~,'~' o o ~n r1 n O O O
O o p O O
O
O O O O O
O O O O O
u7 u7 O ri (r) r-I ~-I N
n O O
r1O
O
N
01f~ N (~ CDQp N O O O N O r-IW ~ W W
r1 ' ~ W FCW W
O O N ~ rlI~~' U) HlW W 1 i r1 M C~ M t~'~ ~ x cex rx ~ ~ ~ ~ ~ ~ ~ ~ W Pa PaO N
~ x ~ s~ ~ ~ ~ o ra f11O -r-I-rl-.-I-~i-rlu1a.-)E-~E-~H , O s~ ~ D 5 ~ D N cn cl~cn U1S-itll (1, ~ ~ ~ ~ ~ ~ O N N
rd S~~ s~ - f.1 O -r-I-r-I-r-I-r-I-r-I,~~ 1 1 1 O
~.IH H H H H ~ z - 1~ -Graph 1 so ,o so tp 2p +, aa.
pfp +
days O
tp +
dpt tp+34Mqs ~, Gr-aph 2 so ,o so 50 ~ 2p ~ tp +
dqs Otp+l4Mys ptp +
Mq~
tp+30dM
~
Mt M2 M4 Mt M2 M3 M4 M5 M7 M8 M10 M17
Mq~
tp+30dM
~
Mt M2 M4 Mt M2 M3 M4 M5 M7 M8 M10 M17
Claims (17)
1, Composition based on a copolymer comprising homo-or copolyamide polyamide blocks and polyether blocks comprising:
a) 500 to 10 000 ppm of at least one phenolic antioxidant;
b) 0 to 5000 ppm of at least one antioxidant based on phosphorus or based on sulphur;
c) 0 to 5000 ppm of at least one UV absorber;
d) 200 to 3000 ppm of at least one methylated hindered amine light stabilizer or HALS and/or 200 to 1300 ppm of at least one nonmethylated HALS;
ppm meaning parts per million of total composition.
a) 500 to 10 000 ppm of at least one phenolic antioxidant;
b) 0 to 5000 ppm of at least one antioxidant based on phosphorus or based on sulphur;
c) 0 to 5000 ppm of at least one UV absorber;
d) 200 to 3000 ppm of at least one methylated hindered amine light stabilizer or HALS and/or 200 to 1300 ppm of at least one nonmethylated HALS;
ppm meaning parts per million of total composition.
2, Composition according to Claim 1, characterized in that the proportion of methylated HALS is from 300 to 2000 ppm.
3, Composition according to either one of the preceding claims, characterized in that the proportion of methylated HALS is from 400 to 1000 ppm.
4, Composition according to any one of the preceding claims, characterized in that the proportion of nonmethylated HALS is from 200 to 800 ppm.
5, Composition according to any one of the preceding claims, characterized in that the proportion of nonmethylated HALS is from 300 to 700 ppm.
6, Composition according to any one of the preceding claims, characterized in that the proportion of (a) is between 2000 and 8000 ppm.
7. Composition according to any one of the preceding claims, characterized in that the proportion of (a) is between 3000 and 6000 ppm.
8. Composition according to any one of the preceding claims, characterized in that the proportion of (b) is between 1000 and 2000 ppm.
9. Composition according to any one of the preceding claims, characterized in that the proportion of (b) is between 1200 and 1700 ppm.
10. Composition according to any one of the preceding claims, characterized in that the proportion of (c) is between 1000 and 2000 ppm.
11. Composition according to any one of the preceding claims, characterized in that the proportion of (c) is between 1200 and 1700 ppm.
12. Composition according to any one of the preceding claims, characterized in that the polyamide blocks are PA 12, PA 11 or PA 6 blocks and the polyether blocks are PTMG, PEG or PPG blocks.
13. Composition according to any one of the preceding claims, characterized in that the phenolic antioxidant (a) is taken from the group consisting of Irganox® 1010, Irganox® 1098 and Irganox® 245.
14. Composition according to any one of the preceding claims, characterized in that the antioxidant of phosphate type or based on sulphur (b) is taken from the group consisting of ADK STAB® PEP 36, ADK
STAB® PEPBHT and Doverphos® 9228.
STAB® PEPBHT and Doverphos® 9228.
15. Composition according to any one of the preceding claims, characterized in that the UV absorber (c) is taken from the group consisting of Tinuvin®
320, Tinuvin® 350 and Tinuvin® 312.
320, Tinuvin® 350 and Tinuvin® 312.
16. Composition according to any one of the preceding claims, characterized in that the HALS (d) is taken from the group consisting of Tinuvin® 765, Tinuvin® 144, ADK STAB® LA52, Chimasorb® 119, Tinuvin® 770 and Nylostob® SEED.
17. Article comprising a composition according to one of the preceding claims.
1g. Use of a composition according to one of Claims 1 to 16 for manufacturing a shoe sole.
1g. Use of a composition according to one of Claims 1 to 16 for manufacturing a shoe sole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0509465A FR2890969A1 (en) | 2005-09-16 | 2005-09-16 | POLYAMIDE BLOCK COPOLYMERS AND AGING RESISTANT POLYETHER BLOCKS |
| FR05/09465 | 2005-09-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2559831A1 CA2559831A1 (en) | 2007-03-16 |
| CA2559831C true CA2559831C (en) | 2010-06-22 |
Family
ID=35945278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2559831 Expired - Fee Related CA2559831C (en) | 2005-09-16 | 2006-09-18 | Ageing-resistant copolymers comprising polyamide blocks and polyether blocks |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9095189B2 (en) |
| EP (1) | EP1767573B1 (en) |
| JP (1) | JP2007084822A (en) |
| CN (1) | CN101024695B (en) |
| CA (1) | CA2559831C (en) |
| FR (1) | FR2890969A1 (en) |
| TW (1) | TWI357429B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202260B1 (en) | 2008-12-23 | 2012-12-12 | Ems-Patent Ag | Inherently stable polyamide elastomer and method for production of same |
| FR2958649B1 (en) * | 2010-04-07 | 2012-05-04 | Arkema France | BLOCK COPOLYMER FROM RENEWABLE MATERIALS AND PROCESS FOR PRODUCING SUCH A BLOCK COPOLYMER |
| CN103665842A (en) * | 2013-11-18 | 2014-03-26 | 安徽宜万丰电器有限公司 | Ultraviolet-proof modified nylon 6 material for automobile plastic parts |
| FR3030535B1 (en) * | 2014-12-19 | 2018-07-27 | Arkema France | COPOLYMER COMPRISING AT LEAST THREE BLOCKS: POLYAMIDE BLOCKS, PEG BLOCKS AND OTHER BLOCKS |
| WO2017098861A1 (en) * | 2015-12-08 | 2017-06-15 | 東レ株式会社 | Moisture-absorbing core-sheath composite yarn, and fabric |
| FR3058724B1 (en) * | 2016-11-14 | 2018-12-07 | Arkema France | EXTRUDABLE POLYMER COMPOSITION IN PERMEABLE OBJECT TO WATER VAPOR |
| MX2019010629A (en) | 2017-03-10 | 2019-12-02 | Advansix Resins & Chemicals Llc | Wire and cable jacket composition of pa6/66 copolymer base resin for improved processability and properties. |
| CN112679728A (en) * | 2020-12-29 | 2021-04-20 | 南京开创新材料科技有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| KR20240097422A (en) * | 2022-12-20 | 2024-06-27 | 에스케이마이크로웍스 주식회사 | Protecting film |
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| JPS6053558A (en) | 1983-09-02 | 1985-03-27 | Toray Ind Inc | Stabilized polyetheresteramide composition |
| JPS60110724A (en) * | 1983-11-18 | 1985-06-17 | Daicel Chem Ind Ltd | Production of polyether-ester-amide |
| US4803894A (en) * | 1984-02-27 | 1989-02-14 | The Shelburne Corporation | Bicycle pedalling apparatus |
| JPS61289119A (en) * | 1985-06-14 | 1986-12-19 | Toray Ind Inc | Elastic fiber and production thereof |
| IT1205023B (en) | 1987-05-22 | 1989-03-10 | Ciba Geigy Spa | PIPERIDIN TRIAZIN COMPOUNDS USABLE AS POLYOLEFIN STABILIZERS |
| JPH086031B2 (en) | 1987-05-23 | 1996-01-24 | 住友化学工業株式会社 | Polyether polyamide composition |
| US5380774A (en) * | 1989-11-28 | 1995-01-10 | Hoechst Celanese Corporation | Nylon molding compositions exhibiting improved protection against UV-light degradation |
| JPH051223A (en) * | 1991-06-27 | 1993-01-08 | Showa Denko Kk | Polyamide resin composition of excellent light resistance |
| JP3048430B2 (en) * | 1991-08-20 | 2000-06-05 | 出光石油化学株式会社 | Polycarbonate resin composition |
| FR2685660A1 (en) * | 1991-12-31 | 1993-07-02 | Atochem | PROCESS FOR PREPARING COMPOSITE MATERIAL FORMED OF A VULCANIZED ELASTOMER ASSOCIATED WITH A THERMOPLASTIC ELASTOMER HAVING A POLYAMIDE SEQUENCE AND COMPOSITE MATERIAL. |
| DE59306328D1 (en) * | 1992-10-21 | 1997-06-05 | Ciba Geigy | Phenyl phosphites as stabilizers for organic materials |
| EP0608976B1 (en) * | 1993-01-08 | 1997-11-12 | Tosoh Corporation | Esteramide copolymers and production thereof |
| US5658984A (en) * | 1994-12-22 | 1997-08-19 | Mitsubishi Engineering-Plastics Corporation | Permanent anti-static polycarbonate resin composition |
| US5900471A (en) | 1997-04-03 | 1999-05-04 | Alliedsignal Inc. | Films of blended nylon resins and laminates therefrom |
| US5969014A (en) * | 1997-09-23 | 1999-10-19 | Clariant Finance (Bvi) Limited | Synergistic polyamide stabilization method |
| JPH11199667A (en) * | 1998-01-14 | 1999-07-27 | Arakawa Chem Ind Co Ltd | Polyether-ester-amide, antistatic agent and thermoplastic resin composition |
| JP3618562B2 (en) * | 1998-11-20 | 2005-02-09 | 株式会社クラレ | Polyamide block copolymer and method for producing the same |
| JP2001031763A (en) * | 1999-07-19 | 2001-02-06 | Sekisui Chem Co Ltd | Polyamide elastomer |
| IT1318423B1 (en) * | 2000-03-24 | 2003-08-25 | Great Lakes Chemical Europ | STABILIZING MIXTURES FOR ORGANIC POLYMERS. |
| CN1222565C (en) * | 2000-05-31 | 2005-10-12 | 西巴特殊化学品控股有限公司 | Stabilizer mixtures |
| US6828364B2 (en) * | 2000-07-14 | 2004-12-07 | Ciba Specialty Chemicals Corporation | Stabilizer mixtures |
| US20020086743A1 (en) * | 2000-10-06 | 2002-07-04 | Bulpett David A. | Urethane elastomers with improved color stability |
| FR2824329B1 (en) * | 2001-05-03 | 2003-06-13 | Atofina | ANTISTATIC POLYMER COMPOSITIONS |
| FR2846332B1 (en) * | 2002-10-23 | 2004-12-03 | Atofina | TRANSPARENT COPOLYMERS WITH POLYAMIDE BLOCKS AND POLYETHER BLOCKS |
-
2005
- 2005-09-16 FR FR0509465A patent/FR2890969A1/en active Pending
-
2006
- 2006-09-08 EP EP06120348.5A patent/EP1767573B1/en active Active
- 2006-09-15 TW TW95134334A patent/TWI357429B/en active
- 2006-09-15 US US11/522,255 patent/US9095189B2/en active Active
- 2006-09-18 CA CA 2559831 patent/CA2559831C/en not_active Expired - Fee Related
- 2006-09-18 CN CN2006100647623A patent/CN101024695B/en active Active
- 2006-09-19 JP JP2006252174A patent/JP2007084822A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN101024695B (en) | 2011-07-27 |
| TWI357429B (en) | 2012-02-01 |
| TW200804515A (en) | 2008-01-16 |
| US9095189B2 (en) | 2015-08-04 |
| EP1767573B1 (en) | 2018-08-01 |
| JP2007084822A (en) | 2007-04-05 |
| EP1767573A1 (en) | 2007-03-28 |
| US20070066725A1 (en) | 2007-03-22 |
| CA2559831A1 (en) | 2007-03-16 |
| CN101024695A (en) | 2007-08-29 |
| FR2890969A1 (en) | 2007-03-23 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140918 |